Silver halide photographic materials

Abstract

A silver halide photographic material is described, comprising an emulsion which is chemical-ripened in the presence of a compound having the formula (I) or (II), ##STR1## wherein R 1 is hydrogen, an alkali metal ion, or an ammonium ion; R 2 is an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an amino group, a substituted amino group, a halogen atom, an acyloxy group, an acylamino group, a carbamoyl group, a nitro group, an aryl group, an allyl group, a sulfo group or a carboxy group; Y represents a divalent linking group; and n is 0, 1, or 2; such emulsions show high sensitivity without fog and have good stability.

What is claimed is: 
     
       1. In a process for producing a silver halide photographic material comprising the steps of (1) a precipitating step of silver halide grains to obtain a silver halide emulsion;   (2) a physical ripening step of the silver halide grains of the silver halide emulsion;   (3) a chemical ripening step of the physical-ripened silver halide grains of the silver halide emulsion;   (4) an adding step of additives to the chemical-ripened silver halide emulsion; and   (5) an coating step of the silver halide emulsion on a support, characterized in that step (3) is conducted in the presence of a noble metal sensitizer and for a compound represented by the formula (I) or (II) ##STR4## wherein R 1  represents hydrogen, an alkali metal ion, or an ammonium ion; R 2  represents an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an amino group, a substituted amino group, a halogen atom, an acyloxy group, an acylamino group, a carbamoyl group, a nitro group, an aryl group, an allyl group, a sulfo group or a carboxy group; Y represents a divalent linking group; and n is 0, 1, or 2.   
     
     
       2. A process for producing a silver halide photographic material as in claim 1, wherein the compound of formula (I) or (II) is added to the silver halide emulsion before a pre-ripening or in a pre-ripening step in an amount of from about 0.05 to 200 g per mol of silver halide. 
     
     
       3. A process for producing a silver halide photographic material as in claim 1, wherein the compound of formula (I) or (II) is added to the silver halide emulsion in a chemical-ripening step in an amount of from about 0.001 to 10 g per mol of silver halide. 
     
     
       4. A silver halide photographic material as in claim 1, wherein said chemical ripening step is conducted in the further presence of a sulfur sensitizer. 
     
     
       5. A process for producing a silver halide photographic material as in claim 1, wherein in formula (I) R 1  represents an alkali metal ion, or an ammonium ion and R 2  represents an alkyl group, an alkoxy group, an acyloxy group, an acyl group, an amino group, a substituted amino group, a halogen atom, an acylamino group, a carbamoyl group, or a carboxyl group. 
     
     
       6. A process for producing a silver halide photographic material as in claim 5, R 2  represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, an amino group, a substituted amino group having total carbon atoms of 1 to 10, a halogen atom, an acylamino group having 1 to 6 carbon atoms, a carbamoyl group having 2 to 10 carbon atoms, or a carboxyl group. 
     
     
       7. A process for producing a silver halide photographic material as in claim 1, wherein in formula (I) n represents 0. 
     
     
       8. A process for producing a silver halide photographic material as in claim 1, wherein the compound of formula (I) or (II) is added to the silver halide emulsion before completion of chemical-ripening. 
     
     
       9. A process for producing a silver halide photographic material as in claim 1, wherein the compound of formula (I) or (II) is added to the silver halide emulsion in a precipitation step of silver halide grains. 
     
     
       10. A process for producing a silver halide photographic material as in claim 1, wherein the compound of formula (I) or (II) is added to the silver halide emulsion in a physical ripening step. 
     
     
       11. A process for producing a silver halide photographic material as in claim 1, wherein the compound of formula (I) or (II) is added to the silver halide emulsion in a chemical-ripening step. 
     
     
       12. A process for producing a silver halide photographic material as in claim 2, wherein the compound of formula (I) or (II) is added to the silver halide emulsion in the pre-ripening step in an amount of from 0.05 to 200 g per mol of silver halide. 
     
     
       13. A process for producing a silver halide photographic material as in claim 12, wherein the compound of formula (I) or (II) is added to the silver halide emulsion in the pre-ripening step in an amount of from 0.1 to 100 g per mol of silver halide. 
     
     
       14. A process for producing a silver halide photographic material as in claim 3, wherein the compound of formula (I) or (II) is added to the silver halide emulsion in the chemical-ripening step in an amount of from 0.005 to 3 g per mol of silver halide. 
     
     
       15. A process for producing a silver halide photographic material as in claim 1, 2, 3, or 4, wherein the amount of compound represented by the formula (I) or (II) in the silver halide emulsion is from 0.001 to 10 g per mol of silver halide. 
     
     
       16. A process for producing a silver halide photographic material as in claim 1, 2, 3, or 4, wherein the amount of compound represented by the formula (I) or (II) in the silver halide emulsion is from 0.005 to 3 g per mol of silver halide. 
     
     
       17. A process for producing a silver halide photographic material as in claim 2, wherein the addition of the compound of formula (I) or (II) is conducted at a temperature of from 30° to 90° C., a pH of from 1 to 11, and a pAg of from 5 to 11. 
     
     
       18. A process for producing a silver halide photographic material as in claim 17, wherein the addition of the compound of formula (I) or (II) is conducted at a temperature of from 40° to 80° C., a pH of from 2 to 9, and a pAg of from 7.8 to 10.5. 
     
     
       19. A process for producing a silver halide photographic material as in claim 3, wherein the compound of formula (I) or (II) is added to the silver halide emulsion at a temperature of from 30° to 80° C., a pH of from 3.0 to 8.5, and a pAg of from 7.0 to 9.5. 
     
     
       20. A process for producing a silver halide photographic material as in claim 19, wherein the compound of formula (I) or (II) is added to the silver halide emulsion at a temperature of from 40° to 70° C., a pH of from 5.0 to 7.5, and a pAg of from 8.0 to 9.3. 
     
     
       21. A process for producing a silver halide photographic material as in claim 1, wherein said noble metal sensitizer is a gold complex salt. 
     
     
       22. A process for producing a silver halide photographic material as in claim 21, wherein said gold complex salt is selected from the group consisting of potassium chloroaurate, potassium aurithiocyanate, auric trichloride and 2-aurosulfobenzothiazole methochloride. 
     
     
       23. A process for producing a silver halide photographic material as in claim 1, 21 or 22, wherein said noble metal sensitizer is used in an amount of from 10 -9  mol to 10 -3  mol per mole of silver halide. 
     
     
       24. A process for producing a silver halide photographic material as in claim 4, wherein said sulfur sensitizer is used in an amount of from 5×10 -6  mol to 10 -2  mol per mol of silver halide. 
     
     
       25. A silver halide photographic material produced by the process of: precipitating silver halide grains to obtain a silver halide emulsion;   ripening the silver halide grains of silver halide emulsion; chemically ripening the physically ripened silver halide grains of the silver halide emulsion;   adding additives to the chemically-ripened silver halide emulsion; and   coating the silver halide emulsion on a support, characterized in that said chemical ripening step is conducted in the presence of a noble metal sensitizer and a compound represented by the formula (I) or (II) ##STR5##  wherein R 1  represents hydrogen, an alkali metal ion, or an ammounium ion; R 2  represents an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an amino group, a substituted amino group, a halogen atom, an acyloxy group, acylamino group, a carbamoyl group, a nitro group, an aryl group, an allyl group, a sulfo group or a carboxy group; Y represents a divalent linking group and n is 0, 1, or 2.